Anthraquinone 1, 2, 4-triazines



United States PatentO 2,967,862 ANTHRAQUINONE 1,2,4-TRIAZINES William L. Berry, Neshanic, and William L. Mosby, North Plainfield, N .J., assignors to American Cyanamizl Company, New York, N.Y., a corporation of Maine N Drawing. Filed Oct. 12, 1959, Ser. No. 845,635 4 Claims. (Cl. 260-249) This invention relates to new anthraquinone 1,2,4-triazines and dihydrotriazines of the structures II N and l N m? m ll NH in which R is the Z-anthraquinonyl radical is formed. When such a compound is treated with a reducing agent, the nitro group upon reduction, eifects a ring closure to form a dihydrotriazine of the structure N HN R O H I NH which is readily oxidized, even during recrystallization, to form the triazine of the formula first given. The reduction of the nitro compound is effected either by an alkaline reagent such as sodium sulfite or by a catalytic hydrogenation, such as with hydrogen over palladium and charcoal. The latter is preferred since the use of sodium sulfide Patented Jan. 10, 1961 always causes the formation of some oxadiazine as well as the dihydrotriazine, due to the alkalinity of the reagent.

The 2-anthraquinonyl carbohydrazides which are used as starting materials are prepared from the various available anthraquinonyl-Z-carboxy chlorides and hydrazine. Examples of Z-anthraquinonyl carboxy chlorides which may be used are the carboxy chlorides of anthraquinone-Z- carboxylic acid, 1-chloroanthraquinone-Z-carboxylic acid, 1 methoxyanthraquinone 2 carboxylic acid, 1 aminoanthraquinone-2-carboxylic acid and the like.

These new 1,2,4-triazines of our invention are useful as vat dyes having very deep shades of reds, violets and blues. They can be used as vat dyes or as vat pigments for the coloration of resins and hydrocarbons such as gasolines. a I

Our invention can be illustrated by the following examples in which parts are by weight unless otherwise specified.

'1 Exampl'e 1 NH, o NH-NH-CO A mixture of 21 parts of 1-chloro-2-nitro-anthraquinone, 20 parts of l-amino anthraquinone-Z-carbohydrazide and 1500 parts by volume of ortho-dichlorobenzene is stirred at C. until the reaction is substantially complete. The reaction mixture is cooled and the dull red solid which separates is'isolated by filtration.

Similarly when equivalent quantities of anthraquinone- 2-carbohydrazide,. 1 chloroanthraquinone 2-carbohydrazide or 1 methoxyanthraquinone 2 carbohydrazide are used in place of the l-aminoanthraquinone-Z-carbohydrazide a similar product is obtained.

Example 2 NH; O N be C O A mixture of 30 parts of the product of Example 1, 50 parts of sodium sulfide nonahydrate and 400 parts of pyridine and 600 parts of water were allowed to stir at room temperature until the reaction Was substantially complete. The deep blue black product is then isolated by filtration and washing. It can be purified by recrystallization from trichlorobenzene.

When the other substituted anthraquinone products described in Example 1 are similarly treated, similar dihydrotriazines are obtained.

Example 3 NH, N N I I I N Example 4 Five parts of the product of Example 3 is milled with 100 parts of polyvinylchloride, 50 parts of di-Z-ethylhexyl phthalate, 2 parts of barium cadmium laurate and 1 part of a triarylphosphite. The milled product is then molded in a standard manner, to yield a deep red brown sheet of polyvinylchloride.

We claim: 1. Compounds of the structure in which R is selected from the group consisting of 2-anthraquinonyl, 1 chloro 2 anthraquinonyl, 1-methoxy-2 anthraquinonyl and l-amino-2-anthraquinonyl.

2. The compound of the formula 4 3. The compounds of the structure N N H R 5 0 l in which R is selected from the group consisting of 2-anthraquinonyl, 1-chloro-2-anthraquinonyl, l-methoxy-Z-an- 5 thraquinonyl, and 1-amino-2-anthraquinonyl.

4. The new compound NH; 0 1% N\ o H 80 References Cited in the file of this patent FOREIGN PATENTS 291,983 Germany Ian. 31, 1914 OTHER REFERENCES Lubs: The Chemistry of Synthetic Dyes and Pigments,

p. 530, Reinhold Publishing Corp. (1955).

Erickson et al.: The 1,2,3- and 1,2,4-triazines, tetrazines and pentazines [vol. 10 of The Chemistry of Heterocyclic Compounds], chapter II, pp. 113-123, Interscience Publishers, Inc., NY. (1956).

UNITED STATES PATENT OFFICE f Certificate of Correction I Patent N 0. 2,967,862

January 10, 1961 William L. Berry et a1.

error appears in the above numbered correction and that the said Le patent requiring tters Patent should read as corrected below. Column 1, lmes 27 to 36, the formula should appear as shown below instead of as in the patent:

N 0 H1( T I NH same column 1, line 70, for sulfite read'-su1fide; column mula should appear as sh 2, lines 20 to 28, the forown below instead of as in the patent:

columtn 3,1mes 20 to 29 the formula should appear as shown below mstead of as m the paten N 0 N T shown below instead of as m the paten 0 same column 3, lines 35 to 44, the right-hand portion of the formula should appear as 0 Signed and sealed this 26th day of September 1961.

[ Attest ERNEST W. SWIDER,

DAVID L. LADD, Atteah'ng Oficer. domm'ssiom of Patents. 

1. COMPOUNDS OF THE STRUCTURE 